Indium oxide (In2O3), tin oxide (SnO2) and indium tin oxide (ITO), have substantial advantages for use as transparent conducting oxides which are employed, for example, in optoelectonic devices, flat panel displays and photovoltaic devices and which are also useful in gas sensors and as catalysts. In these types of applications, it can be helpful for device performance to have precise control over film thickness and composition, and some applications require the ability to coat high aspect ratio geometries or porous materials. In2O3 thin films can be deposited using a variety of methods including sputtering, chemical vapor deposition, and atomic layer deposition (ALD). Of these techniques, ALD shows the most significant promise as this method affords excellent control over both the thickness and the composition of the deposited film. Most importantly, ALD offers excellent deposition conformality that enables the coating of porous materials with aspect ratios in excess of 1000.
Previously, In2O3 deposition by ALD has been accomplished using InCl3 with either H2O or H2O2 as the oxygen source. Although useful for coating planar surfaces, this method suffers from several limitations. First, the InCl3 chemistry requires high growth temperatures of ˜300-500° C. and yields a low growth rate of only 0.25-0.40 Å/cycle. In addition, the InCl3 has a very low vapor pressure and must be heated to 285° C. just to saturate a planar surface. Furthermore, the corrosive HCl byproduct can damage the deposition equipment. But the greatest limitation of the InCl3/H2O method, especially for coating nanoporous materials, is that InCl3 can etch the deposited In2O3. Consequently, nanoporous materials require very long precursor exposures that are likely to completely remove the In2O3 from the outer portions of the nanoporous substrate.
An improved ALD process for In2O3 has also been sought for many years and a number of alternate precursors have been investigated including β-diketonates (In(hfac)3 (hfac=hexafluoropentadionate), In(thd)3 (thd=2,2,6,6-tetramethyl-3,5-heptanedioneate), and In(acac)3 (acac=2,4-pentanedionate)) and trimethyl indium, (In(CH3)3). Unfortunately, these efforts were unsuccessful. No growth was observed using β-diketonates with water or hydrogen peroxide, while trimethyl indium did not yield self-limiting growth.